Patent GB-821937-A (GB)
Title: New dithiophosphoric acids and derivatives thereof and process for their manufacture
IPC: C07F9/165
Filed: 1955-10-03
Abstract: Mineral oil compositions contain dithiophosphoric acids of the general formula <FORM:0821937/III/1> wherein R represents an aliphatic, aromatic or aliphatic-aromatic residue containing not more than 20 carbon atoms, any of which may contain a halogen atom, R1 represents hydrogen or a residue as defined under R, and X represents an oxygen or sulphur atom, or salts of such acids such as the oleylamine salt, or di-, tri- or tetrasulphides derived from such acids by reaction with sulphuryl chloride, sulphur dichloride or sulphur monochloride respectively, or esters of such acids obtained by reacting the acids with alkylene oxides, or thiol-thionophosphoric acids obtained by reacting the aforesaid esters with phosphorus pentasulphide.  It is preferred to add from 1 to 5% by weight of said compounds to the mineral oil.  Typical compounds of the above general formula are b  : b  - di - (o : o - dibutyl - dithiophosphoric acid)-diethyl - tetrathiophosphoric acid, b  : b  - di(S : S - dibutyl - tetrathiophosphoric acid) - diethyl - tetrathiophosphoric acid, and b  : b 1 - di(o : o - di - n - octyl - dithiophosphoric acid) - diethyl - thiolthionophosphoric acid, and a typical polysulphide is sym-bis-[1 : 11-di-(o : o-di - n - butyl - dithiophosphoric acid) - 3 : 31-dichlorodipropyl - 2 : 21 - thionophosphoric acid] tetra-sulphide.ALSO:The invention comprises dithiophosphoric acids of the general formula <FORM:0821937/IV (a)/1> wherein R represents an aliphatic, aromatic or aliphatic-aromatic residue containing not more than 20 carbon atoms, any of which may contain halogen, R1 represents hydrogen or a residue as defined under R, and X represents a oxygen or sulphur atom, and the preparation thereof by reacting a thiolthiono-phosphoric acid of the general formula <FORM:0821937/IV (a)/2> wherein R and X have the above significance, with the required ethylene oxide or sulphide and the resulting ester is reacted with phosphorus pentasulphide.  The invention also comprises salts of the above dithiophosphoric acids, di-, tri- and penta-sulphides obtained by reacting the above dithiophosphoric acids with sulphuryl chloride, sulphur dichloride and sulphur mono-chloride respectively, esters of the above dithiophosphoric acids obtained by reacting the acids with alkylene oxides, and thiol-thionophosphoric acids obtained by reaction the above dithiophosphoric acids with phosphorus pentasulphide.  Salts of the above dithiophosphoric acids may be the alkali metal, alkaline earth metal and heavy metal salts, and salts with amines such as oleylamine.  In the examples: (1) b  : b 1 - (O : O - di - n - butyl - dithiophosphoric acid) - diethyl - thiolthionophosphoric acid (the oleylamine salt is also referred to) is prepared by reacting ethyl oxide with O : O-din-butyl-thiolthionophosphoric acid, and reacting the resulting 1-(O : O-di-n-butyl-dithiophosphoric acid)-ethanol-(2) with phosphorus pentasulphide; (2) 1 : 11-di-(O : O-di-n-butyl-dithiophosphoric acid) - 3 : 31 - dichlorodipropyl (2 : 21)-thiolthionophosphoric acid is prepared by reacting O : O-di-n-butyl-thiolthionophosphoric acid and epichlorhydrin, and reacting the resulting 1 - (O : O - di - n - butyl - dithiophosphoric acid)-3-chloropropane-ol-(2) with phosphorus pentasulphide; the product may be converted into a tetrasulphide by reaction with the calculated quantity of sulphur monochloride, the tetrasulphide being described as sym.-bis[1 : 11 - di - (O : O - di - n - butyl - dithiophosphoric acid) - 3 : 31 - dichlorodipropyl - (2 : 21) - thiono - phosphoric acid] - tetrasulphide; (3) b  : b 1 - di - [O : O - di - (4 - chlorophenyl) - dithiophosphoric acid] - a  : a 1 - diphenyldiethyl - thiolthiono-phosphoric (the oleylamine salt is also referred to) is prepared as in (1), b -[O : O-di-(4-chlorophenyl) - thiolthionophosphoric acid] - a  - phenyl-ethanol being the intermediate compound obtained by reacting phenyl-ethylene oxide with O : O - di - (4 - chlorophenyl) - thiolthionophosphoric acid; (4) b : b  - di - (O : O - dibutyl - dithio - phosphoric acid) - diethyl - tetrathiophosphoric acid is prepared by reacting O : O-dibutyl-thiolthionophosphoric acid with ethylene sulphide to form O : O-dibutyl-dithiophosphoric acid S-(b -mercaptoethyl)-ester and reacting this ester with phosphorus pentasulphide; (5) b ,b -di-(S : S-dibutyl-tetrahiophosphoric acid)-diethyl-tetrathiophosphoric acid is prepared by reacting S : S-dibutyl-tetrathiophosphoric acid with ethylene sulphide to form S : S-dibutyl-tetrathiophosphoric acid S-(b -mercaptoethyl)-ester and reacting this ester with phosphorus pentasulphide.